CN1938876A - An organic electronic device and methods for manufacturing a device of this kind - Google Patents

An organic electronic device and methods for manufacturing a device of this kind Download PDF

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Publication number
CN1938876A
CN1938876A CNA2005800097345A CN200580009734A CN1938876A CN 1938876 A CN1938876 A CN 1938876A CN A2005800097345 A CNA2005800097345 A CN A2005800097345A CN 200580009734 A CN200580009734 A CN 200580009734A CN 1938876 A CN1938876 A CN 1938876A
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based device
intermediate layer
organic based
electroactive
organic
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Inventor
M·桑德伯格
P·-E·诺达尔
G·格雷茨恩斯基
M·乔翰逊
P·卡尔森
H·G·古德森
G·古斯塔夫森
L·安德森
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FILM ELECTRONIC Co Ltd
Ensurge Micropower ASA
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FILM ELECTRONIC Co Ltd
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
    • G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
    • G11C13/0009—RRAM elements whose operation depends upon chemical change
    • G11C13/0014—RRAM elements whose operation depends upon chemical change comprising cells based on organic memory material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
    • G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
    • G11C13/0009—RRAM elements whose operation depends upon chemical change
    • G11C13/0014—RRAM elements whose operation depends upon chemical change comprising cells based on organic memory material
    • G11C13/0016—RRAM elements whose operation depends upon chemical change comprising cells based on organic memory material comprising polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C2213/00—Indexing scheme relating to G11C13/00 for features not covered by this group
    • G11C2213/50—Resistive cell structure aspects
    • G11C2213/55—Structure including two electrodes, a memory active layer and at least two other layers which can be a passive or source or reservoir layer or a less doped memory active layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/311—Purifying organic semiconductor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers

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  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Semiconductor Memories (AREA)
  • Thin Film Transistor (AREA)
  • Formation Of Insulating Films (AREA)
  • Electroluminescent Light Sources (AREA)
  • Photovoltaic Devices (AREA)
  • Bipolar Transistors (AREA)

Abstract

An organic electronic device consists of one or more electro-active organic or polymer materials sandwiched between electrodes. Critical in such devices is the interface between the electrode and the polymer, where degradation or chemical reaction products may develop that are deleterious to the proper functioning of the device. This is solved by introducing a functional interlayer composed of one or more materials consisting of a molecular backbone bearing phosphonate or phosphate functions, either directly attached or through side chains, said functional layer being disposed between at least one of the respective electrodes and said one or more electro-active materials in the device.

Description

The method of organic based device and this equipment of manufacturing
The present invention relates to organic based device, comprising can be with the electroactive organic material of physics or chemical mode response when standing electric field or electric current, wherein this electroactive material is set in the layer structure between first group and the second group of respective electrode, wherein in electroactive material, define directly electrical access or of unit with electric capacity shape structure and this unit, and wherein each unit can be visited selectively to cause electroactive response via electrode electrical access indirectly.
The invention still further relates to the method for making this equipment.
The present invention be more particularly directed to some when using simultaneously, show the favourable electrical property and the organic group material of chemical property with the object of needs dominations electric charge and equipment.More specifically, the present invention relates to the purposes of this type of organic group material in thin film electronic equipment, described thin film electronic equipment contains can be with the electroactive organic material of physics or chemical mode response when standing electric field or electric current, and be particularly related to memory device, wherein this equipment comprises the organic storage medium that shows electret or ferroelectric performance.This storage medium is set in the layer structure between first group and the second group of respective electrode usually, defines the unit with electric capacity shape structure thus.This unit is electrical access or via electrode electrical access indirectly directly, and the normally array of similar units or the part of matrix, and wherein each unit can be used for carrying out in selected unit and write, reads or erase operation by visit selectively.This electrode is made by one of various metal or alloy usually, and described metal or alloy has in some cases and formed oxidation film etc. by surface modification.By the conductibility organic material, for example conjugated polymer manufacturing electrode also is possible.
FAQs in the equipment of electrode contact organic material is therein, and chemistry and/or physical process take place at the electrode interface place, or occur in the device fabrication process, otherwise in the operation of equipment process as the result of electric stress (curtage).These processes may produce undesirable influence, and scope is from the diminish performance to the bust.
It is to provide organic or inorganic intermediate layer between electrode and thin polymer film that a class that has caused concern is remedied.This intermediate layer will have various functions, and in order to emphasize this on the one hand, this type of intermediate layer will be known as " functional intermediate layer " from now in this article.Therefore, the barrier flaps effect will be for example played in the intermediate layer, make by showing inertia and impermeable obstruct or by reacting with adjacent material in a controlled manner, being avoided the harmful chemical reaction between electrode and the electroactive organic material.Another function in intermediate layer can provide the protection at contingent physical damage in the metal deposition process that is undertaken by sputter.
The intermediate layer example of the insertion of report is the oxide of various metals, for example TiO x, perhaps nitride, for example TiN has typically represented stoichiometric fine and close boundary zone.The inorganic intermediate layer material has the relevance with inorganic and organic electroactive material.
Importantly recognize, except that their permeability, chemical reactivity, cost, toxicity, machinability etc., the relevant in this article equipment of all types is basically also proposed very special requirement to the electric property in this class intermediate layer.Especially, the memory cell in electric capacity shape structure is flimsy, thereby forms " extremely " layer for example chemical reaction product at the electrode place, they be electric insulation and low-k arranged.The low electric capacity that each " extremely " layer representative is connected with memory cell, the cell voltage that is applied that causes reducing ratio is transmitted on the storage substance that is applied in the unit, causes worse performance.
Discussed in the applicant's total pending application application and the problem that is used to store the intermediate layer electric property relevant with the thin film electronic equipment of display application, wherein this equipment comprises electroactive organic or polymeric material.A characteristic that can provide in the functional intermediate layer that forms for specific purpose is electrode is extended into effectively and to pass low resistance or big electric capacity in the frequency field of being concerned about in intermediate layer.
Based on organic material, particularly electroactive organic material is being used in the functional intermediate layer of oligomer and polymer, and for example the equipment aspect of ferroelectric polymer and oligomer acquires a special sense.Functional intermediate layer material can be classified as high dielectric constant insulator or have the conductor of low complex impedance under relevant frequency.In one classification of back, people can define the material with high electron conductivity or have the subclassification of the material of high proton conductivity.Polypyrrole (PPY), polyaniline (PANI), polythiophene or other the heterocycle polymer material of first kind example for mixing, and the example in other classification comprises for example by the poly-ethylidene dioxy base thiophene (PEDOT) of polystyrolsulfon acid (PSSH) and derivative doping thereof.
The functional intermediate layer of organic group has shown and is difficult to realize in physical storage devices up to now.Except when be difficult to keep outside chemical integrity and the barrier property when in operating process, standing electric stress, especially also exist and reach and keep gratifying electric property, the i.e. subject matter of the low complex impedance in the intermediate layer under relevant frequency: on the one hand, in being similar to the process of mixing, electronic conductor is damaged easily in the process of top electrodes deposition.On the other hand, the proton hydrate conductor relies on water to keep their conductance and/or high capacitance usually, and this makes them at high temperature be faced with dehydration.Dehydration may become under 80-100 ℃ significantly being starkly lower than, and causes that the conductance of functional layer and/or electric capacity significantly reduce.The conductance in the intermediate layer and/or the loss of electric capacity have destroyed the expectation function in functional intermediate layer, make functional intermediate layer itself become " dead layer ".
In view of the foregoing, a main purpose of the present invention is to record and narrate the material of Special Category, it is suitable for being introduced into the thin film electronic equipment that contains electroactive organic material, particularly contains in the memory device of electret or ferroelectric organic material as functional intermediate layer.These intermediate layers must run through equipment life, even after operating after the storage duration or in dry environment and/or under the high temperature, also keep high conductivity and/or dielectric constant.
Another purpose provides the instruction to method and process detail, and it is the important success factor in the memory device of introducing the functional intermediate layer of the present invention is made.
According to the present invention, above-mentioned purpose and further feature and advantage are utilized, and organic/electronic equipment is realized, described organic/electronic equipment further comprises at least one functional intermediate layer of being made up of one or more materials, described one or more materials comprise the molecular moiety of phosphonic acids or phosphate group or its salt, wherein under any circumstance, a functional intermediate layer is set between the electroactive organic material of at least one described electrode and described interface, and wherein under situation about being provided with more than an intermediate layer, described intermediate layer can have similar or different compositions.
In first preferred embodiment, organic based device is a non-volatile memory device, electroactive material be have ferroelectric or electret properties and can show hysteresis or retentivity can electropolarized dielectric storage medium, and the memory cell in the non-volatile memory device forms the element of active matrix or passive matrix, making the electroactive response that causes constitute writes/reads/erase operation, this operates in sets up required polarized state or carries out its polarization conversion in the memory cell, and makes the clear and definite polarized state of setting up in memory cell determine its logic state.
In second preferred embodiment, described organic based device is a luminaire, and described electroactive material is luminescent material, makes when excited by electric field or electric current, and the electroactive response formation that is caused is luminous.
In the 3rd preferred embodiment, described organic based device is an electric capacity, and functional intermediate layer itself constitutes electroactive material.
According to the present invention, above-mentioned purpose and further feature and advantage also utilize the method for making organic based device to realize, thus, first method feature is by the functional intermediate layer material of one of following technology deposition: the self assembly of the polyeletrolyte of spin coating, evaporation, sputter, chemical vapor deposition (CVD), physical vapor deposition, oppositely charged or successively (LBL) that replaces deposition or the LBL structure that is formed by metal phosphonic acid salt chemistry; Another method feature is to make at least a stabilisation in the functional intermediate layer material and/or it can not be dissolved; And another method feature is to make at least one patterning in the functional intermediate layer at last; Described method independence or combination are carried out.
According to appended dependent claims, further feature and advantage will be conspicuous.
Describe the present invention in detail referring now to accompanying drawing,
Fig. 1 represents the general electric capacity shape structure relevant with the present invention,
Fig. 2 is and the similar structure of Fig. 1, forms " dead layer " at the interface afterwards at each electrode/storage medium,
Fig. 3 is and the similar structure of Fig. 1, but has the functional layer of inserting between each electrode and the accumulation layer of the present invention now,
Fig. 4 a demonstration is compared with the organic intermediate layer of another kind, based on the thermal stability of the dielectric constant that gathers (vinyl phosphonate) functional intermediate layer (PVPA),
Fig. 4 b shows and to compare with the equipment with another kind of organic intermediate layer, and the equipment that contains the functional intermediate layer of PVPA base is in the hole aperture after 16 hours (eye opening) (difference between the impulse response of logical one and 0) under 70 ℃,
Fig. 5 a, 5b and 5c are examples of polymer of the present invention,
Fig. 6 be the expression preferred embodiment of the invention equipment profile and
Fig. 7 is the important step in making according to the passive addressable matrix device of the preferred embodiment of the invention.
The present invention's basic thought and feature behind can be illustrated and discuss by the common apparatus structure with reference to figure 1 illustrated at first.Particularly, this structure can be represented for example according to the basic unit of storage in the data storage device of prior art.Described electroactive material in this case, shows the polarization retentivity and therefore can play the ferroelectric of storage substance effect or the electret organic material is clipped between two electrodes in the electric capacity shape structure.By apply voltage signal between electrode, storage medium is subjected to influencing or to inquire about the electric field of its polarized state.In physical device, a lot of unit are made side by side with array on solid substrate commonly used.Usually, each unit is made in proper order,, and finally reaches on the top that comparative electrode wherein is deposited on sandwich and forms the step that will be known as " top electrodes " subsequently near electrode (being called " bottom electrode " the presents) beginning of base material from.
Fig. 2 is presented at and stands common chemistry that runs into and/or the unit among the Fig. 1 after the electric stress in manufacturing and operation duration process: therein in the boundary zone of the electroactive material in the electrode osculating element, form " dead layer ", the performance of weary electrode of damned break or electroactive material, and the unit performance is reduced.Usually, dead layer is the chemical reaction product of low conductivity and dielectric constant (" low ε "), makes dead layer show as the parasitic capacitance with units in series.
Fig. 3 demonstration is similar to the unit that shows among Fig. 1, but now according to the present invention, has wherein formed functional intermediate layer between electrode and electroactive material.This point realizes by the special-purpose deposition step in the unit process for making usually, but also can append by post-depositional controlled reaction.Although the basic thought of Fig. 3 illustrated is not new, the present invention is taught in the intermediate layer and uses the Special Category material, as will be in following detailed description.
In Fig. 4 illustrated the improvement to equipment performance that can realize by the function of use intermediate layer, it is presented at the result who obtains in the memory cell based on the ferroelectric copolymer relevant with device fabrication, wherein as the result of long-time operation at high temperature, (Fig. 4 a) is associated in the reduction of unit degraded and the dielectric constant in the intermediate layer at electrode place.Shown in Fig. 4 b, use is based on the polymerization phosphonic acids according to the present invention functional intermediate layer of (gathering (vinyl phosphonate) (PVPA)), compare with other same unit that contains other organic intermediate layer as the corresponding candidate testing of materials, excellent performance is provided: in this embodiment, the storage medium in the unit is polarized corresponding to logic state " 0 " or " 1 ".As can be seen, in having stood 70 ℃ of unit of 16 hours, show good contrast (" hole aperture ") between " 0 " and the one state for the current response of inquiry potential pulse, and the contrast unit has lost the hole aperture after same treatment with PVPA.
To do in more detail the present invention now and describe.According to the present invention, at first will determine to constitute the fundamental type of the material in functional intermediate layer, illustrate then how these intermediate layers can form film in the electric capacity shape structure of being concerned about.Describe the fusible method in intensity, temperature tolerance and intermediate layer and the material improvement of promoting functional intermediate layer, and provided several embodiment preferred.
The material that forms basis of the present invention comprises the organic molecule that has phosphonic acids or phosphate group.This molecule normally is suitable for the polymeric material based on the processing of solution, perhaps be suitable for gas deposition than micromolecule.Phosphonic acids or phosphoric acid material can be homopolymers, copolymer, blend polymer or its salt, and phosphonic acids or phosphate group can directly or via the side chain that is fit to be connected to molecular backbone.This polymer can obtain by mode progressively and by chain polymerization.Latter's type is preferred, because they can have highdensity phosphonic acids or phosphate group.In addition, the performance of the middle layer composition of polymerization can improve by introducing additive.
When providing as the thin intermediate layer in the electric capacity shape structure, and stand may be at relevant device, during the various stress that for example runs under the operating condition of the memory cell shown in Fig. 3, having now found that with other many materials of comparing this general remark of previously known provides good equipment performance.This point can be to a certain extent a plurality of functions by described material be illustrated.
Herein, should should be mentioned that and report poly-(vinyl phosphonate), make it be suitable for polymer electrolyte film (WO03075389) even (PVPA) under high temperature and low humidity, also can show high proton conductivity.Therefore, reasonably be that expection phosphonic acids or phosphate group participate in providing and have the anti-functional intermediate layer of observed low resistance, even in dry environment and under the high temperature (for example 80 ℃).This point is one of desirable characteristics of this type of layer, as pointing out in the above introduction.
Many functional intermediate layer materials of the present invention have high-k concurrently, therefore have low intermediate layer electric capacity and high ohmage.This point is in addition favourable application in relating to the situation of ultra-thin electroactive layer, is used for eliminating because the danger of the electric short circuit of defective in the electroactive layer or hole or electric leakage path.
When the unit that top electrodes is applied to shown in Fig. 1, there is the danger that destroys electroactive material.The protection that provides this infringement has been provided in functional intermediate layer of the present invention, makes that the degree of freedom is bigger in the selection of electro-deposition and Patternized technique and material.
Backbone molecule part can be by providing anchoring for phosphonic acids or phosphate group, and by interacting with the measurable and controlled way intermediate layer with adjacency, and functional intermediate layer is stablized, the intermediate layer of described adjacency comprises electroactive material and electrode surface.According to the selection that sandwiches together to the material in the fixed structure, this point can provide the chemical stability and the adhesiveness of enhancing in interlayer region, as pointing out in more detail following.At last, molecular moiety provides chance for various performances are cropped in the functional intermediate layer.The example of this point is the temperature characterisitic that possible influence relevant devices.
To discuss middle layer composition in more detail now.
Functional intermediate layer can be homopolymers and the copolymer with phosphonic acids or phosphate group and other functional group, or these blend.
The general example of these kind materials is shown in the following structure.
Figure A20058000973400141
Figure A20058000973400151
X=PO 3H 2Or PO 4H 2,
X1=PO 3H 2, PO 4H 2, H or alkyl
X2=PO 3H -Or PO 4H -
Z＝PO 3H 2、PO 4H 2、PO 3HR、COOH、COOR、OR、CONHR、CONR 2，
D＝(CH 2) p、O(CH 2) p、COO(CH 2) p、CO(OCH 2CH 2) p、CONH、S(CH 2) p、N(CH 2) p、Ar、O-Ar、CH 2Ar、(CH 2) pCHY、(CH 2) pY(CH 2) o
D＝(CH 2) p、COO、COO(CH 2) p、CO(OCH 2CH 2) p、CONH、O、S、N、Ar、O-Ar、CH 2Ar、(CH 2) pCHY、(CH 2) pY(CH 2) o
D1＝(CH 2) p
D2＝(CH 2) p、(CH 2) pS(CH 2) 2、(CH 2) pS(CH 2) 3
Y=alkyl or PO 3H 2, COOH
R1=H, alkyl, PO 3H 2, PO 4H 2, PO 3HR, COOH, COOR, OR, CONHR, CONR 2, CONH 2,
R2=R3=H, alkyl, PO 3H 2, PO 4H 2, CONH 2
R4＝H、COOH、COOR
R5＝H、COOH
R6＝H
The R7=alkyl or aryl
The R8=alkyl or aryl
The R9=alkyl or aryl
The R10=alkyl or aryl
The R=alkyl
A＝COO、CONH、NHCONH、NHCOO、O、CO
B＝OCO、NHCO、OCONH、NHCONH、O、CO
The big number of n=, the repetitive in expression polymer or the oligomer
0＜x＜1
o＝0、1、2、3....
p＝0、1、2、3....
Figure A20058000973400161
X=-PO 3H 2Or-O-PO 3H 2
Y=H, alkyl or-PO 3H 2Or-O-PO 3H 2
Z=H, alkyl or-PO 3H 2Or-O-PO 3H 2
A=alkyl, Ar ,-O ,-S ,-NR ,-CO-,-COO-,-CONR-,-NRCOO-,-NRCONR-
B＝-CH 2、-O、-S、-NR、-CO-O、-CO-NR
R 1, R 2, R 3, R 4=H, alkyl, Ar ,-PO 3H 2,-OPO 3H 2,-COOR ,-CONR 2,-COR ,-OR,
R 5, R 6=alkyl, aryl or heteroaryl
Ar=aryl or heteroaryl
R=H or alkyl
m＝0、1、2、3--
n＝1、2、3、4----
p＝0、1
q＝0、1
r＝0、1、2、3--
s＝0、1
t＝0、1、2---
The example of homopolymers comprises by the polymer of the monomer with one or more phosphonic acids or phosphate group with the monomer preparation with phosphonic acids and another kind of functional group.With regard to the phosphoric acid of polymerization, people can use the polymerization alcohol phosphate.Example is: poly-(vinyl phosphoric acid), poly-(isopropenyl phosphoric acid) and other poly-(alkenyl phosphoric acid), poly-(pi-allyl phosphonic acids).Other example is: polyacrylate, polyacrylamide, poly epihydric alcohol base ether or ester or poly-(styrene) with phosphonic acids or phosphate group; poly-(1, the 1-EDP), poly-(2-(phosphonomethyl) acrylic acid) and corresponding acrylate or acrylamide.
Among copolymer, people can use the copolymer that comprises two or more the dissimilar repetitives with phosphonic acids or phosphate group.The serve as reasons copolymer of monomer below at least two kinds preparation of example: vinyl phosphonate, pi-allyl phosphonic acids, alkenyl phosphoric acid, isopropenyl phosphoric acid, 1 for example, has phosphonate ester or phosphate-based styrene at the 1-EDP.
People also can use the copolymer that comprises phosphonic acids or phosphate group and have the repetitive of other functional group (improving for example processing or adhesion properties).This group can be phosphonate ester, carboxylic acid or ester, Carboxylamide, amine, sulfoxide, sulfone, sulfonic acid, ether, thioether and alkyl or perfluoroalkyl chain.
Example for poly-(vinyl phosphonate-altogether-acrylic acid) and corresponding acrylate, poly-(vinyl phosphonate-altogether-methacrylic acid) and corresponding methacrylate, use gather (vinyl alcohol) of phosphoric acid partial esterification.
The copolymer of phosphonic acids and phosphonate ester can obtain by the partial hydrolysis of polymeric phosphines acid esters, homopolymers and copolymer, and perhaps the direct copolymerization by phosphonic acids and phosphonate ester obtains.Ester group is selected,, and can be contained list and diester so that give the electric and processing characteristics that material is fit to.An example is poly-(vinyl phosphonate-be total to-(the single ethyl vinyl phosphonate ester of O-)).
Functional intermediate layer also can be made up of the blend of described polymer, and different thus polymerization phosphonic acids or phosphoric acid are by blend or wherein polymerization phosphonic acids or phosphoric acid and other oligomeric or polymeric material blend.The latter can be contained and is subjected to the proton group, for example polyvinyl alcohol, polyvinyl acetate base ester, poly propenoic acid acrylate, polyacrylamide or polyurethane, polyester, polyamide, polyethers, poly-imines, polymethyl vinyl ether-maleic acid, polyvinylpyrrolidone, polyacrylonitrile, cellulose or cellulose acetate.Contain phosphonate ester or phosphate-based polymer also can with similar polythiophene, for example the electroactive polymer of PEDOT mixes.Have been found that when containing the phosphonic acids polymer concentration and substantially exceed 50%, blend shows good electronics and processing characteristics.But the size in the zone that is separated can be greater than the structure of using in the modern electronic equipment.The example of the blend that is fit to comprises poly-(vinyl phosphonate)-blend-poly-(acrylic acid) (PAA), and the ratio of the mixture of preferred PVPA and PAA is or near 90: 10.Other example comprises poly-(vinyl phosphonate)-blend-poly-(methacrylic acid), poly-(vinyl phosphonate)-blend-poly-(maleic acid), poly-(vinyl phosphonate)-blend-poly-(styrene sulfonic acid), poly-(vinyl phosphonate-altogether-acrylic acid)-blend-poly-(acrylic acid), poly-(vinyl phosphonate-altogether-acrylic acid)-blend-poly-(methacrylic acid), poly-(vinyl phosphonate-altogether-acrylic acid)-blend-poly-(maleic acid), poly-(vinyl phosphonate-altogether-acrylic acid)-blend-poly-(styrene sulfonic acid).
Containing phosphonate ester or phosphate-based polymer can use with the form of mixtures of pure acid or salt corresponding with it, described salt is and for example alkali metal, alkaline-earth metal, Zn, Al, Ti, Zr, Hf, perhaps with organic substance, the for example amine of alkyl or polymeric amine, for example poly-aminobenzene ethene, polyvinyl or PAH, polydiene propyl group amine or the polyethylene imine based salt of polyvinylpyridine, polyvinyl pyrroles, replacement.
In these materials some have high-k at kilohertz in the mhz frequency scope, in some cases with the combination of high-ohmic resistance rate.As amorphous with homogeneous, these materials are structurally simple than other the known high-k organic material that contains crystal region usually.This point for successfully prepare under the pattern of sub-micron level on form and layout the ultrathin film of the sharp outline of homogeneous be important, referring to following.
Phosphonic acids and some metal ions form strong complex.Phosphonic acid metal salt, the particularly stability of phosphonic acids zirconium are the bases except that promising successively (LBL) deposition technique that is used for having occurred a plurality of prior arts of the layer by layer deposition of self assembly mercaptan on the precious metal surface or oppositely charged polyeletrolyte.Corresponding reference is based on M-P chemistry:Zhang, Y., and Clearfield, A., 2821 pages of Inorg.Chem.31 phases (1992), and Cao, G., Lee, H., Lynch, V.M., Mallouk, T.E., Inorg.Chem., 27 phases 2781 pages (1988)).The polymerization phosphonic acids of mentioning in this patent assists the LBL reaction mechanism mechanism of reaction of the zirconium-phosphonate of (spin-assisted) to deposit smoothly by spin coating, produces the intermediate layer with acceptable energy.The example of the Zr-P deposition that spin coating is auxiliary then carries out rinsing for deposition and cross-linked polymeric phosphonic acids, is exposed to zirconium oxychloride solution and repeats rinsing.This circulation can repeat, to produce structurally well-defined intermediate layer.
The polymer of this paper can be used for forming structure by the alternating deposit successively of the polyeletrolyte of oppositely charged.(referring to, for example: G.Decher:Layered Nanoarchitecturesvia Directed Assembly of Anionic and Cationic Molecules "; Comprehensive Supramolecular Chemistry, Vol., " Templating, Self-Assembly and Self-Orgnaization, J.-P.Sauvage andM.W.Hosseini (eds.), Pergamon Press, Oxford, 1996,507-528).
Example is polymeric acid and polymerization alkali structure alternately, wherein polymeric acid is poly-(vinyl phosphonate) or poly-(vinyl phosphonate-be total to-acrylic acid) or poly-(vinyl phosphonate-be total to-(O-monoalkyl vinylphosphonate)), and wherein polymerization alkali is polyethylene imine based or the polyimides pyrroles.Another family of phosphine or phosphorus sill is the ionene class.Example is the polymeric ammonium salts with low-molecular-weight phosphonic acids or phosphoric acid.
Micromolecule with phosphonic acids or phosphate has sufficiently high vapour pressure so that gas deposition is feasible.Phosphonic acids and can also can in the equipment described in this patent, form functional intermediate layer with the alternating deposit that phosphonic acids forms the molecule of complex compound.
A representative example of intermediate layer material of the present invention is a vinyl phosphonate (VPA) and the copolymer of acrylic acid (AA), and copolymer p (VPA-is common-and AA) (70: 30).This material shows low complex impedance, even under anhydrous state and under the high temperature, for example under 80 ℃.It also shows high-k (300-500) at 10kHz in the 100kHz frequency range.
Electrode and its material in the organic based device of the present invention will be discussed now in more detail.The material of some kinds can be used as and functional intermediate layer electrodes in contact.But a requirement is the product that must avoid possible.In addition, can select material and processing conditions, it is anti-to make that product has low resistance.Therefore, the decline that keeps the electric field strength in the low for example memory cell.Specially suitable electrode material is Au, Pt, Pd, Al or Ti.Prevent that the another kind of method that high impedance areas forms from being to introduce barrier layer (for example oxide or nitride) between electrode and functional intermediate layer.Under the sort of situation, also have other electrode material more suitable than above-mentioned those.Have in the face of the electrode based on titanium/titanium dioxide combination of the oxide in functional intermediate layer is verified and can be used for connecting, for example the memory device of electroactive material based on polymeric ferroelectrics.Other example of suitable barrier layer is oxide and/or refractory metal nitride, for example TiN and TaN ".
Top electrodes can be formed by distinct methods.It should be noted that the interface that does not allow between irradiation, plasma, heating equivalent damage top electrodes and the functional intermediate layer of deposition process itself.The typical sedimentary technology comprises chemical vapor deposition (CVD) physical vapor deposition (PVD) or sputter.
The deposition that is manufactured on of electronic equipment of the present invention needs the technology that is fit in the intermediate layer.Also may require to use post-depositional technology, so that improve the stability in the intermediate layer of deposition.The deposition of functional intermediate layer material can be undertaken by one of following technology: the self assembly of the polyeletrolyte of spin coating, evaporation, sputter, chemical vapor deposition (CVD), physical vapor deposition, oppositely charged or successively (LBL) that replaces deposition or the LBL structure that is formed by the phosphonic acid metal salt chemistry.
Noncrystalline degree is formed on the prerequisite of the ultrathin film of form homogeneity under the pattern of sub-micron level typically, also is the prerequisite of making the fine pattern structure in physical device.With regard to steric regularity, most of phosphorous acid esters described herein and phosphonate polymer are not optionally, cause negligible degree of crystallinity.
Obtaining homogeneous film by spin coating proceeding is the task of requirement, and it is in controlled atmosphere, for example N 2Or implement easily in other inert gas.This method provides high reproducibility, and is a kind of very simple method on the whole.In addition, spin coating can be carried out in vacuum chamber.
Also can further carry out preliminary treatment to each layer before the deposition.Therefore, before further deposit thin film layers or electrode, can use peroxide, particularly H 2O 2Handle bottom electrode (BE) or top electrodes (TE).The form of PVPA of Sheng Chaning or common P (VPA-AA) film and the topological structure pattern uniformity that depends on solution concentration, the speed of rotation and practical basis medium for example.
The mixture of PVPA and its copolymer water soluble and water and alcohol.Usually, must always there be some water.The effect of alcohol is the humidity that strengthens the bottom hydrophobic film.The solvent that is fit to is that for example 1-propyl alcohol (NPA) or 2-propyl alcohol (IPA) or trifluoroethanol and water are represented preferred value with the mixture of 90: 10 to 50: 50 ratio at 70: 30.
Be their solubility in water based on the relevant subject matter in many intermediate layers of polymeric phosphines or phosphorus.This point makes needs they and common high power capacity manufacturing process contradiction to wash with water wafer or wafer is carried out some follow-up dissolvings based on deposition step between procedure of processing in described manufacturing process.Functional intermediate layer may be damaged or remove to this point.Therefore, need improve to stablize described polymeric layer and to make it water insoluble.This purpose may be attended by and for example make crosslinked polymer.Crosslinked also have strengthen the fusible effect of intermediate layer material.
For the intermediate layer of expecting in this patent, crosslinked can being undertaken by heat or hardening with radiation intermediate layer can be added chemicals thus, and promptly so-called crosslinking agent is to increase the degree of cross linking.
This chemicals can be to have the molecule that forms two or more functional groups of covalent bond with polymer that will be crosslinked.At this these are called molecule crosslinked dose.Its also can be with polymer in two or more groups of existing form the ion of complex compounds, connect polymer with ionic bond thus.
For some metal oxide base material, only heated polymerizable Phosphoric acid or phosphonic acid film can make film soluble effectively, a kind of in fact the use and disclosed technology.This reagent also can be the group that exists in the initiated polymerization thing, and perhaps the formation interpenetrating networks of Cun Zaiing effectively make the initator of the insoluble monomer polymerization reactions of composite material that obtains.These chemical cross-linking methods need at high temperature cure to finish crosslinked usually.Also possible is to be with or without under the situation of above-mentioned crosslinking agent, to cause crosslinked by the irradiation polymerization thing.
Below be the preferred cross-linking method that provides and the example of reagent.
Embodiment 1: hot curing
For some middle layer composition, heat treatment is enough.This point is true especially under the situation of the base material of for example aluminium, is known for the such curing that gathers (vinyl phosphonate-be total to-acrylic acid).
For other polymerization middle layer composition and other base material, it may be necessary adding crosslinking agent.Have been found that the molecule that has two or more epoxide groups can be used for crosslinked middle layer composition, copolymer or the blend that also contains hydroxy-acid group except containing phosphonic acids or phosphate.Have been found that this composition with diepoxides becomes soluble after heat treatment.The example of this epoxides is the diglycidyl ether of (DGE), alkane, and for example the ether of butanediol diglycidyl ether, glycidyl end-blocking for example gathers or low polyethylene glycol or rudimentary ethylene glycol.Triglycidyl group glycerin ether (TGG), triglycidyl group isocyanuric acid ester (TGIC), aromatic glycidyl ethers, for example diglycidyl cresols (DGC) or for example diglycidyl ether, the N of benzene dimethanol, N-diglycidylaniline, N, N-diglycidyl-4-glycidyl oxygen base aniline, polycarboxylic triglycidyl group oxygen base benzene glycidyl esters.In addition, can use the glycidyl ether and the ester of polymerization.
Embodiment 2: ion crosslinking agent
The intermediate layer can be exposed to metal complex, cause the formation of the phosphonic acid metal salt complex compound that polymer chain is linked together.The example that can be used for the metal complex that dissolves in organic solvent in crosslinked intermediate layer based on polymeric phosphines acid comprises zirconic chloride, bromide and iodide, ZrCl 4, acetopyruvic acid titanium oxide or four alkyl dioxides.
Amine, particularly two or polyfunctional amine can be added in the middle layer composition to form the polymer chain of ionic crosslinking.The example comprises the amine of aliphatic series or aromatic diamine or polyamines or polymerization.
Embodiment 3: adopt the photoactivation additive to carry out crosslinked on middle layer composition by irradiation
1. use for example AIBN or peroxide, for example isopropyl benzene hydroperoxide, tert-butyl peroxide or dibenzoyl peroxide, heat or UV initiated polymerization thing are crosslinked.
2. when ultraviolet irradiation, the molecule that contains two or more azidos can crosslinked middle layer composition.
Embodiment 4: undertaken crosslinked by forming IPN
For example AIBN or peroxide are used in heat or UV initiation reaction, and diallyl sulfone or divinylsulfone, or amine, for example diallylamine, or diallyl acid amides, for example 1,3-diallyl urea or N, N-DATD or use the divinyl benzene derivative.Use description to crosslinked some preferred embodiment of reading of the present invention now.They comprise:
A): heat cross-linking, use polyepoxides, DEB for example, the diepoxy hexane, diglycidyl ether (DGE), the diglycidyl alkyl ether, for example glycidol 1, ammediol, the poly(ethylene oxide) of glycidyl end-blocking or corresponding oligomer (DGPEO), triglycidyl group glycerol (TGG), triglycidyl group isocyanuric acid ester (TGIC), aromatic glycidyl ethers, for example glycidol phenol (DGC) or for example diglycidyl ether of benzene dimethanol, N, the N-diglycidylaniline, N, N-glycidol-4-glycidyl oxygen base aniline, triglycidyl group oxygen base benzene or polycarboxylic glycidyl esters.
Figure A20058000973400221
B): heat causes crosslinked, uses polyisocyanates, for example aromatics two isocyano benzene, two isocyano ortho-xylenes, or aliphat polyisocyanic acid root alkane, for example 1,4-two isocyano propane or 1,6-two isocyano hexanes.
Isocyanates
Ar: aromatics or heteroaromatic rings
Ar_NCO) n Ar_CH 2-NCO) n Alk_NCO) n
Alk: alkyl
C): the reaction that heat or UV cause, use for example AIBN or peroxide, and diallyl sulfone or divinylsulfone, or amine, for example diallylamine, or diallyl acid amides, for example 1,3-diallyl urea or N, N-DATD or use the divinyl benzene derivative.
Pi-allyl and vinyl sulfone
Figure A20058000973400232
Allylamine and acid amides
D): it is crosslinked that heat or UV cause, and uses the poly-nitrine that replaces, for example benzene disulfonyl base, benzene three sulfonyl nitrine, xyxylene sulfonyl nitrine or benzene three sulfonyl nitrine.
Sulfonyl azide
Ar: aromatics or heteroaromatic rings
Ar-[SO 2N 3] n Ar-[CH 2-SO 2N 3] n Alk-[SO 2N 3] n
Alk: alkyl
E): the crosslinked polymer that heat or UV cause, use for example AIBN or peroxide, for example isopropyl benzene hydroperoxide, tert-butyl peroxide or dibenzoyl peroxide.
Some polymeric acid and the adhesiveness between the adjacent material that are used for intermediate layer described in this patent may be very bad, produce processing problems.Therefore, importantly be identified for improving fusible method between functional intermediate layer and the adjacent material, described adjacent material may be for example electrode or hydrophobic polymer.Simultaneously, be used for improving fusible method and should do not give bad Electronic Performance at equipment.Adhesiveness between intermediate layer and the adjoining course can be by with chemistry or physics mode modification base material, i.e. so-called priming and being improved.In addition, can be by as the comonomer in the copolymer, give good adhesiveness as the blend polymer component or as the suitable functional group that surfactant additive is introduced.
Below pay close attention to the example that preferred adhesiveness is improved technology and material.
Embodiment 6: prime
Priming polymeric substrate or electrode with the adhesiveness improved the intermediate layer can be to produce functional group in polymeric substrate, for example processing of epoxy radicals, peroxide, carboxylic acid, aldehyde, ketone, amino, hydroxyl.
Epoxy radicals can be for example by using peroxide or peroxy acid, two key oxidations of existing in the polymeric substrate are produced.Introduce two keys and can be the start-up portion of technology of priming.
Carboxylic acid and other carbonyl and alcohol radical and peroxide also can use ozone treatment to be produced by two keys.Hydroxyl also can be obtained by two keys.
Two keys are present in the base material usually natively, introduce them preparatively but also can have.
Epoxy radicals can be to be used to be connected middle layer composition with the effective same way as of epoxy radicals crosslinking agent.Carboxyl, acid amides, ester, alcohol, amine and mercapto can pass through modified surface polarity, by with middle layer composition in carboxyl form dimer, acid anhydrides, acid amides and ester, perhaps by using metal-phosphonate chemistry, by with the intermediate layer in polymer chain form complex compound and improve adhesiveness the intermediate layer.
Embodiment 7: copolymer
With some homopolymers to hydrophobicity or hydrophilic surface demonstration poor bonding, for example poly-(vinyl phosphonate) compared, and the copolymer that is prepared by vinyl phosphonate and other monomer has better adhesiveness.Compare with homopolymers poly-(vinyl phosphonate), the example that hydrophobic surface is had the fusible copolymer of improvement is the copolymer of vinyl phosphonate and following monomer
Vinylphosphonate,
Acrylic acid,
Methacrylic acid,
The ester of acrylic or methacrylic acid,
Vinyl ethers,
Phosmers TM。
Embodiment 8: blend
Compare with homopolymers poly-(vinyl phosphonate), hydrophobicity or hydrophilic surface are had improvement fusible blend example for poly-(vinyl phosphonate) with
Poly-(acrylic acid),
Poly-(methacrylic acid),
Poly-(maleic acid),
The blend of poly-(vinyl phosphonate) of partial esterification.
Embodiment 9: improve fusible additive
Improve fusible additive and can be the molecule of giving the excellent adhesion of the hydrophobic layer of adjacency, its react in case with covalent connect and/or provide with middle layer composition in the physical bond of polymer molecule.
The example of this molecule is
Alkyl glycidyl base ether,
The fluoroalkyl glycidyl ether.
The polyepoxide crosslinking agent of other example for mentioning in the paragraph formerly, it has shown the same adhesiveness of improving.
They also can be the molecule that only plays Action of Surfactant, for example Zonyl-F.
In some cases, be total to electroactive organic material and the functional intermediate layer that annealing makes polymerization by making material carry out heat, for example the adhesiveness at the interface between the PVPA significantly improves.
May making up of excellent adhesion/good film morphology can be the deposition of using a kind of alternative spin coating.In this, a kind of method is to use metal-phosphonate (MP) chemistry.This method allows to produce thin film, and the form of improvement and less surface tension consistency problem are compared in this film demonstration with spin-coating method.Determined that the Zr-P chemistry is comparable to the firm layer of LB film, the method for polyelectrolyte that replaces and SAM layer as preparation.The method that for example is used for the irreversible deposition of the Zr modification of the preferred electrode embodiment of PVPA (TiO) combination and follow-up phosphonic acids is simple, allows the PVPA monolayer deposition on Ti/TiO.The technology that relates to the Zr processing can be: ZrOCl 2Handled (10mM is in MeOEtIMe) 10 minutes, washing is exposed to 0.3%PVPA solution, stays insoluble PVPA layer like this on etched memory films.
Referring now to specific embodiment the adhesiveness that some exemplary materials makes up is discussed, because the correlation of described combination of materials in physical device, it has special meaning.
Embodiment 10
Bottom electrode (BE) and contain phosphonic acids or the functional boundary layer of phosphoric acid polymerization thing between adhesiveness.
A) Ti/TiO-electrode
Phosphonate ester and phosphate ester polymer usually show the excellent adhesion to the Ti/TiO surface, their copolymer or and polar polymer, for example the blend of polyacrylate, polyacrylamide and analogue compounds is like this equally.
For the interface between modification bottom electrode and the intermediate layer, can before applying polymerization phosphonic acids or phosphoric acid intermediate layer, prime for the Ti/TiO electrode by used additives.
This auxiliary agent can be vinyl phosphonate, dihydroxylic alcohols and polyalcohol, have the epoxy compounds of suitable functional group or contain zirconates or complex compound, for example zirconium oxychloride or zirconium chloride.
B) noble metal electrode
Can be by with sulfydryl aryl-or alkyl-amine or acid amides to the adhesiveness of for example Au electrode, comprise cysteine or cysteine oligomer, mercaptoalkyl ethylene glycol or alkyl sulfydryl phosphonic acids/phosphoric acid preliminary treatment and obtain.Here also observe the SAM effect.
Example is 1,1 '-biphenyl-4-sulfydryl-4 '-phosphonate ester or analog, it has the many aromatics or the heteroaromatic chain of further extension.
Embodiment 11
Contain the functional boundary layer of phosphonic acids or phosphoric acid and the adhesiveness between the electroactive film.
Based on the common excellent adhesion that shows above-mentioned phosphorous acid esters/phosphonate polymer, copolymer or blend of the electroactive material of acid amides or heteroaromatic polymers function.
Fluorine-containing electroactive layer shows gratifying adhesiveness to the function interface layer that contains polyacrylate or analog, and estimation may be because favourable dipole-dipole interaction.The adhesiveness of improving can be in addition by make phosphate/phosphonate ester layer more " close fluorine " obtain.The surface modification of functional intermediate layer film also can realize by making itself and fluorinated alkyl epoxides or the reaction of perfluoroalkyl glycidol ether.Parent fluorine surface also can by graft acrylic acid perfluoroalkyl ester on functional interlayer surfaces or polyhexafluoropropylene oxide phosphate (Zonyl-fluorine surfactant) or perfluoroalkyl-sulphonic acid ester or-carboxylate obtains.This surface also can be by with perfluoroalkyl halogenation thing alkylation or by use fluorinated ketone, for example Hexafluoro acetone, hexafluoroacetylacetone acid hydrochlorate or octafluoro-2,4-acetyl butyryl processing and carry out modification.
Embodiment 12
Electroactive film and contain phosphonic acids or the functional boundary layer of phosphoric acid between adhesiveness.
Poor bonding between electroactive film substrate and the phosphonic acids crown center layer may make and be difficult to deposit by spin coating, particularly for extremely thin crown center layer.Electroactive film can be used peroxide, for example H by at deposition crown center layer or before being exposed to ozone 2O 2Or metachloroperbenzoic acid is handled and is primed.Found that also electroactive film can rotate with poly-(vinyl phosphonate-be total to-acrylic acid) processing, follows and polyepoxides or epoxy alkyl or the reaction of aryl phosphine acid esters.Polyacrylate shows the excellent adhesion to electroactive film usually, so expands the top layer that contains PAA or similar polymer, obtains gratifying adhesiveness.Use perfluoroalkyl phosphonate ester or phosphate, for example the Zonyl-fluorine surfactant improves adhesiveness equally.
Embodiment 13
Contain the adhesiveness between phosphonic acids or phosphoric acid function interface layer and the top electrodes.
A) Ti/TiO-electrode
Equally when as copolymer or with the blend of for example polyacrylate and similar polymer, between the polymer of Ti/TiO and phosphorous acid esters/phosphonate ester, obtain excellent adhesion usually.
B) noble metal electrode
In this case, if at first use compounds containing thiol groups (oligomer and polymer), for example alkyl or aryl sulfydryl phosphonate ester or phosphate, sulphonic acid ester or carboxylate are handled film surface, can obtain adhesiveness so.
In order to improve or strengthen the performance of organic based device of the present invention, some operation for this purpose can the key step in device fabrication between or carry out afterwards.Acid/alkali treatment is verified to provide a kind of mode to be used to influence the equipment performance of having introduced material film of the present invention.This principle must be applied according to each independent situation especially.Therefore, verified is to exist alkali to be harmful to equipment performance aspect at least two in the interlayer structure: the first, and alkali may reduce the electric capacity in functional intermediate layer.The second, and be more serious, the existence of alkali may cause in equipment running process for example to form dead layer in the zone relevant with polarization conversion in the ferroelectric storage is used after being exposed to electric field repeatedly.
An important example of acid/alkali treatment will be described now.This is a kind of technology that after this will be known as " acid is reset ", can be used for repairing the damage operation of the photo-etching technological process of the equipment of introducing the functional intermediate layer of the present invention: the physical device of introducing many for example unit shown in Fig. 3 needs the electrode of patterning usually, and wherein said unit other Local Force Company in equipment is received electronic circuit.According to the Patternized technique that is used for upper electrode set, it may change or damage the functional intermediate layer below it.Under many circumstances, the latter becomes in the Patternized technique process, and (functional intermediate layer materials more of the present invention do not show any significant ohmic conduction rate in exposure, and therefore can be applied in all sidedly between electroactive material and the electrode, not belong to generation electric leakage problem between the electrode of different units).If the patterning of top electrodes is undertaken by the conventional wet engraving method, like this may major injury functional intermediate layer, described conventional wet engraving method relates to use alkali, for example uses photoresist remover commonly used.Particularly, will adopt the polymer that contains VPA in the functional intermediate layer that acid replacement technology is illustrated:
The alkali pollution that contains phosphonic acids/phosphate group polymer is a kind of reversible process.Therefore, for example for the PVPA film that pollutes by amine, determined that they can be by being exposed to the exterior layer of removable solution composition by polymeric acid or polymeric acid or low molecular weight acid, by using sour remapping method, wherein preferably use PVPA or stronger polymeric acid, for example poly-(styrene sulfonic acid), PSSH are reclaimed.Protonated alkali migration enters removable acid layer, and proton moves along opposite direction simultaneously.After the certain hour, remove extract layer by washing.It may be necessary repeating this step.
Referring now to the various preferred embodiments of in conjunction with the production method and the material of application organic based device of the present invention being discussed simultaneously.
Preferred embodiment
In Fig. 6 illustrated preferred embodiment, it shows the profile explanation of non-volatile memory cells described in the present invention.It below is the example that is used to make a kind of method of this memory cell.Form bottom electrode by chemical vapor deposition (CVD), physical vapor deposition (PVD) or sputter, and with mask and conventional etching technique for example active-ion-etch or wet etching patterning.In one embodiment, bottom electrode is one group of aluminium and titanium, and its barrier layer that is prevented from formation high impedance interface between metal and the functional intermediate layer covers.The thickness of aluminium and titanium depends on the capacity requirement of photoetching technique and speed and storage.In one embodiment, barrier layer is the titanium dioxide of 50_-100_.After bottom electrode patternization, remove mask by conventional resist stripping means.On bottom electrode and base material, deposit the first functional intermediate layer then comprehensively.In one embodiment, functional intermediate layer is based on carry out spin coating with the polymeric phosphines acid solution of crosslinking agent blend in the alcohol and water mixture.The concentration of copolymer is preferably 0.2-1% in the solvent, and crosslinking agent is 1 to polymer ratio: 10-1: 40.Be rotated in the nitrogen environment with 1500rpm and carry out 30s to 60s to the rotating speed of 4000rpm.The thickness in the first functional intermediate layer can be 50-500_.After the deposition of ground floor, cure subsequently to stablize this layer.Functional layer can be patterning or patterning not, depend on memory capacity and performance impedance behavior to functional intermediate layer.In a preferred embodiment, keeping this layer to make it is not form pattern.Under similar rotating condition, allow ferroelectric store aggregated thing be deposited on the functional intermediate layer comprehensively.Accumulation layer can have 200 to 2000_ thickness.The ferroelectric accumulation layer contains one or more polymer, copolymer or the electret that shows electric polarization magnetic remanence.Then the second functional intermediate layer (needn't be identical with ground floor) is deposited on the ferroelectric accumulation layer with the similar mode in the formation first functional intermediate layer.In a preferred embodiment, before the deposition second functional intermediate layer, carry out the H of ferroelectric accumulation layer 2O 2Handle.
Then whole stacked body is annealed.Best annealing temperature is 100-160 ℃.The thickness in the second functional intermediate layer can be 50-500_.On the second functional intermediate layer, form pattern by PVD deposition top electrodes and by mask and conventional etching technique.In one embodiment, top electrodes is made up of the barrier layer that covers with one or more metal levels.Barrier layer can be the titanium dioxide of 50-100_.
Variously contain phosphonic acids polymer or blend polymer, and water-based solvent can be used to form functional intermediate layer.In one embodiment, polymer is a kind of copolymer of being made up of poly-(vinyl phosphonate-be total to-acrylic acid) (P (VPA-AA)).Ratio between VPA and the AA is preferably 50: 50 to 90: 10.In another embodiment, functional intermediate layer is based on 85: 15 to 95: 5 PVPA and the blend of PAA.In one embodiment, crosslinking agent is poly-(ethylene glycol) diglycidyl ether (PEG-DGE).In another embodiment, crosslinking agent is 1,4-butanediol-diglycidyl ether Bu-DGE.
In a further preferred embodiment, passive matrix visit storage or display device contain the unit of general structure shown in Fig. 3, and the infall of described unit between two groups of parallel strip electrodes forms, as illustrated in fig. 7.In this preferred embodiment, before applying functional intermediate layer, with the volume filling insulating material between bottom and/or the top electrodes.Insulating material has low-k usually, will produce significant favourable influence to the whole electrical characteristics of passive matrix access means in some cases, for example by reducing interelectrode capacitance and electric leakage.Fig. 7 represents to form the basic step of structure: at first (Fig. 7 (1)), on base material, place one group of bottom electrode by standard photolithography techniques or other method, and the processing of the electrode performance in the equipment that randomly electrode surface is carried out enhancing is finished.Follow by deposition step (Fig. 7 (2)), wherein gaps between electrodes usefulness is insulated, the material of preferred low-k is filled.This can typically relate to comprehensive deposition of same coated electrode.Next step, with the polishing of CMP for example, planar surface and exposed electrode material (Fig. 7 (3)) perhaps randomly stay the film of insulating material on electrode with the surface.Apply comprehensive layer (" organic interface " among Fig. 7 (4)) of functional intermediate layer material then.By comprehensive deposition electroactive material, for example under the memory device situation ferroelectric copolymer (referring to " memory films " among Fig. 7 (5)), and the top layer of functional intermediate layer material (" organic interface " among Fig. 7 (6)) makes the remainder of structure, and the material of described top layer needn't be identical with the material in the functional intermediate layer of using at the bottom electrode place.Apply upper electrode set by lithography technique for example in conjunction with the sputter or the evaporation of electrode metal then, produce the structure shown in Fig. 7 (7 and 8).In these steps, functional intermediate layer material can help to protect following material to avoid infringement from photoetching technique or electro-deposition technology.Then then randomly being similar to the mode of filling space between the bottom electrode, with insulation, the material that is generally low-k is filled the space between the top electrodes.To form under the situation of new construction on the structure that so forms therein, can polish top surface is suitable in the laminated apparatus further photoetching technique or application step with formation flat surfaces.
Though the present invention is described according to some selected application, it will be apparent to one skilled in the art that above-mentioned material and technology will have application potential in some other occasions, comprising:
I) as the antistatic film on printing paper and the film; ii) as antisatic additive to insulating material; the iii) high dielectric constant material in the capacitor; iv) be used for organic light emission and display device; v) be used for electromechanical transducer and transducer; comprise the electrode on the loudspeaker; vi) be used for fuel cell; vii) be used for photoetching technique; viii) be used for electrochemical sensor, ix) be used for ion analysis, x) be used for the antistatic protection of electronic circuit; xi) be used for battery; xii) as the surfactant of dispersant and polymer, xiii) be used for the material of drug delivery devices and pharmaceutical formulation, xiv) be used for ion extractuin; the material of uranium for example is xv) as antimicrobial coating; textile coating and as refractory material.

Claims (55)

1. organic based device, comprising can be with the electroactive organic material of physics or chemical mode response when standing electric field or electric current, wherein this electroactive material is set in the layer structure between first group and the second group of respective electrode, wherein in electroactive material, define directly electrical access or of unit with electric capacity shape structure and this unit via described electrode electrical access indirectly, wherein each unit can be visited selectively to cause electroactive response, and further comprise the functional intermediate layer that at least one is made up of one or more materials, described one or more materials comprise the molecular moiety that is connected to phosphonic acids or phosphate group or its salt, wherein under any circumstance a functional intermediate layer is set between the electroactive organic material of at least one described electrode and described interface, and wherein when providing more than an intermediate layer, described intermediate layer can have similar or different compositions.
2. according to the organic based device of claim 1, it is characterized in that this organic based device is a non-volatile memory device, described electroactive material be have ferroelectric or electret properties and can show hysteresis or retentivity can electropolarized dielectric storage medium, and the memory cell in the non-volatile memory device forms the element of active matrix or passive matrix, making the electroactive response that causes constitute writes/reads/erase operation, this operates in sets up required polarized state or carries out its polarization conversion in the memory cell, and makes the clear and definite polarized state of setting up in memory cell determine its logic state.
3. according to the organic based device of claim 1, it is characterized in that this organic based device is a luminaire, wherein electroactive material is a luminescent material, makes the electroactive response that is caused when excited by electric field or electric current constitute luminous.
4. according to the organic based device of claim 1, it is characterized in that described molecular electronic equipment is electric capacity, wherein functional intermediate layer itself constitutes electroactive material.
5. according to the organic based device of claim 1, it is characterized in that described electroactive organic material is made up of single molecule, oligomer, homopolymers, copolymer or its blend or compound.
6. according to the organic based device of claim 1, it is characterized in that described functional intermediate layer material is made up of single molecule, oligomer, homopolymers, copolymer or its blend or compound.
7. according to the organic based device of claim 1, it is characterized in that described molecular moiety comprises the molecule of following form: RP, wherein R represents that organic molecule and P represent one or more phosphonic acids or phosphate group or its salt.
8. according to the organic based device of claim 1, it is characterized in that described molecular moiety comprises the polymer with phosphonic acids or phosphate group or its salt.
9. organic based device according to Claim 8 is characterized in that described polymer is one or more in following: polyvinyls, polyacrylate, polyacrylamide, polyethers, poly epihydric alcohol base ether and/or ester, polyester, polyether-ketone, polyamide, polyurethane or polyureas.
10. organic based device according to Claim 8 is characterized in that described phosphonic acids or phosphate group or its salt are connected on the main polymer chain via acid amides, urethanes, amine, ester, carbonic ester or ether.
11., it is characterized in that described molecular moiety comprises the homopolymers of the monomer with one or more phosphonic acids or phosphonyl group or its salt according to the organic based device of claim 1.
12. organic based device according to claim 11; it is characterized in that described homopolymers is one or more in following: poly-[1-phosphonic acids-1; 2-ethane two bases]; more generally be called poly-(vinyl phosphonate) or PVPA; or pi-allyl phosphonic acids; alkenyl phosphonic acid, isopropenyl phosphoric acid, 1 for example, the homopolymers of 1-EDP or acrylic acid 2-(phosphonomethyl) ester.
13. according to the organic based device of claim 11, it is characterized in that described monomer be in the following type one or more: vinyl, ethenylidene, alkenyl, acrylates or acrylic acid, acrylate, methacrylic acid, methacrylate, acrylate, acrylamide, vinyl ethers, glycidol ether and/or ester and styrene.
14., it is characterized in that described monomer comprises that one or more are used to improve adhesiveness and/or realize crosslinked or otherwise promote other functional group of processing according to the organic based device of claim 11.
15. according to the organic based device of claim 1, it is characterized in that described molecular moiety comprises the copolymer of two or more comonomers, and at least a among the latter has phosphonic acids or phosphate group or its salt.
16., it is characterized in that described comonomer is one or more in the following type: vinyl, ethenylidene, alkenyl, acrylates or acrylic acid, methacrylic acid, methacrylate, acrylate, acrylamide, vinyl ethers, glycidol ether and/or ester and styrene according to the organic based device of claim 15.
17., it is characterized in that one or more comonomers comprise that one or more are used to improve adhesiveness and/or make material compositions soluble or otherwise promote the functional group of processing according to the organic based device of claim 15.
18., it is characterized in that described functional group is one or more in following: the monoesters of carboxylic acid, carboxylate, phosphonic acids or phosphoric acid and diester, fluoroalkyl chain or ether according to the organic based device of claim 16.
19., it is characterized in that described copolymer is poly-(vinyl phosphonate-altogether-acrylic acid) (P (VPA-common-AA)) according to the organic based device of claim 15.
20. according to the organic based device of claim 19, the percentage by weight that it is characterized in that vinyl phosphonate is 50% to 100%.
21. according to the organic based device of claim 15, it is characterized in that described molecular moiety comprises monomer with phosphonic acids and the copolymer with monomer of phosphonate ester, described ester is the monoesters or the diester of phosphonic acids.
22. according to the organic based device of claim 21, the copolymer that it is characterized in that phosphonate ester and phosphonic acids is that the partial hydrolysis by the phosphonic acids of polymerization forms.
23., it is characterized in that described molecular moiety is included in the blend polymer that contains one or more polymer with phosphonic acids or phosphate group and/or its ester or salt according to the organic based device of claim 1.
24., it is characterized in that at least a polymer has one or more and is used to improve adhesiveness and/or makes material compositions soluble or otherwise promote the functional group of processing according to the organic based device of claim 23.
25., it is characterized in that described functional group is one or more in following: the monoesters of carboxylic acid, carboxylate, acid amides, phosphonic acids or phosphoric acid and diester, ether, alcohol or phenol, mercaptan or amine according to the organic based device of claim 24.
26. according to the organic based device of claim 23, it is characterized in that a kind of polymer for gathering (vinyl phosphonate) (PVPA), another kind of polymer is poly-(maleic acid).
27. according to the organic based device of claim 23, it is characterized in that a kind of polymer for gathering (vinyl phosphonate) (PVPA), another kind of polymer is poly-(methacrylic acid).
28. according to the organic based device of claim 23, it is characterized in that a kind of polymer for gathering (vinyl phosphonate) (PVPA), another kind of polymer is for gathering (acrylic acid) (PAA).
29. the organic based device according to claim 28 is characterized in that PVPA: the weight ratio of PAA is in 85: 15 to 95: 5 scope.
30., it is characterized in that described salt comprises one or more in following according to the organic based device of claim 1: alkali metal, alkaline-earth metal, Zn, Al, Ti, Zr, general substituted imidazole and triazole, ammonia, general alkyl-or polyvinylamine, PAH, the polydiene propyl group amine and polyethylene imine based of the poly-aminobenzene ethene of the amine of aryl-replacement, polyvinylpyridine, general replacement, general replacement.
31. according to the organic based device of claim 1, the thickness that it is characterized in that functional intermediate layer, top is in the scope of 50-500_.
32. according to the organic based device of claim 1, the thickness that it is characterized in that functional intermediate layer, bottom is less than 500_.
33., it is characterized in that in the described functional intermediate layer at least one withstand the degraded in the electro-deposition process according to the organic based device of claim 1.
34., it is characterized in that selecting described electrode material to make them form interface with the reaction of functional intermediate layer in a controlled manner with high complex dielectric permittivity according to the organic based device of claim 1.
35., it is characterized in that material at least one described electrode is one or more in the following element: Au, Pt, Pd, Ti or Al according to the organic based device of claim 1.
36., it is characterized in that at least one described electrode is by Ti or Ti/TiO according to the organic based device of claim 1 xForm.
37., it is characterized in that between electrode and functional intermediate layer, protective layer being set according to the organic based device of claim 1.
38., it is characterized in that described protective layer is oxide or nitride according to the organic based device of claim 29.
39., it is characterized in that in the described functional intermediate layer at least one is patterned according to the organic based device of claim 1.
40. according to the organic based device of claim 1, it is characterized in that described organic based device comprises to be arranged on lip-deep parallel striped electrode, and insulating material be set on described surface and it is flushed with electrode in the crack betwixt.
41. method of making organic based device, described organic based device comprises can be with the electroactive organic material of physics or chemical mode response when standing electric field or electric current, wherein this electroactive material is set in the layer structure between first group and the second group of corresponding electrode, wherein in electroactive material, define directly electrical access or of unit with electric capacity shape structure and this unit via described electrode electrical access indirectly, wherein each unit can be visited selectively to cause electroactive response, and further comprise at least one functional intermediate layer of forming by one or more materials, described one or more materials comprise the molecular moiety that is connected to phosphonic acids or phosphate group or its salt, and wherein under any circumstance a functional intermediate layer be set between the electroactive organic material of at least one described electrode and described interface, it is characterized in that by this functional intermediate layer material of one of following technology deposition: spin coating, evaporation, sputter, chemical vapor deposition (CVD), physical vapor deposition, the self assembly of the polyeletrolyte of oppositely charged or successively (LBL) deposition that replaces or the LBL structure of building by the phosphonic acid metal salt chemistry.
42. according to the method for claim 41, wherein said functional intermediate layer material is characterized in that by spin-on deposition spin coating occurs in the vacuum chamber.
43. according to the method for claim 41, wherein said functional intermediate layer material is characterized in that by spin-on deposition spin coating occurs in by in one or more atmosphere formed in following gas or the steam: N 2, inert gas, rare gas or one or more spin-on material and solvent steam.
44. according to the method for claim 41, wherein said functional intermediate layer material is characterized in that using the spin coating solution of heating by spin-on deposition.
45. according to the method for claim 41, wherein said functional intermediate layer material is characterized in that using the solvent as water and one or more pure mixtures by spin-on deposition.
46. according to the method for claim 45, it is characterized in that described mixture is 1-propyl alcohol and/or 2-propyl alcohol and/or 2,2,2-trifluoroethanol and water, and the pure weight ratio to water of selection is 50: 50 to 90: 10.
47. according to the method for claim 41, wherein functional intermediate layer material is characterized in that using peroxide, for example H by spin-on deposition 2O 2Or alkyl-or aryl-peroxide preliminary treatment deposition surface.
48. method of making organic based device, described organic based device comprises can be with the electroactive organic material of physics or chemical mode response when standing electric field or electric current, wherein said electroactive material is set in the layer structure between the respective electrode of first group and second group, wherein in electroactive material, define directly electrical access or of unit with electric capacity shape structure and this unit via described electrode electrical access indirectly, wherein each unit can be visited selectively to cause electroactive response, and further comprise at least one functional intermediate layer of forming by one or more materials, described one or more materials comprise the molecular moiety that is connected to phosphonic acids or phosphate group or its salt, and wherein under any circumstance a functional intermediate layer be set between the electroactive organic material of at least one described electrode and described interface, it is characterized in that making at least one stabilisation in the functional intermediate layer material and/or it can not be dissolved.
49., it is characterized in that in functional intermediate layer material, comprising corsslinking molecular and cause crosslinked after the deposition reaction by heating or irradiation according to the method for claim 48.
50., it is characterized in that using crosslinking agent to promote the stability in functional intermediate layer and/or reduce its solubility according to the method for claim 48.
51., it is characterized in that described corsslinking molecular has two or more epoxide groups according to the method for claim 49.
52., it is characterized in that using the reaction of heat initiation to carry out crosslinked according to the method for claim 49.
53., it is characterized in that using the reaction of UV initiation to carry out crosslinked according to the method for claim 49.
54. method of making organic based device, described organic based device comprises can be with the electroactive organic material of physics or chemical mode response when standing electric field or electric current, wherein said electroactive material is set in the layer structure between first group and the second group of respective electrode, wherein in electroactive material, define directly electrical access or of unit with electric capacity shape structure and this unit via electrode electrical access indirectly, wherein each unit can be visited selectively to cause electroactive response, and further comprise at least one functional intermediate layer of forming by one or more materials, described one or more materials comprise the molecular moiety that is connected to phosphonic acids or phosphate group or its salt, and wherein under any circumstance a functional intermediate layer be set between the electroactive organic material of at least one described electrode and described interface, it is characterized in that making at least one patterning in the described functional intermediate layer.
55., it is characterized in that using hard mask to carry out described patterning according to the method for claim 54.
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